EP0466392B1 - Synthese von hydrophoben alkoxylierten Polymeren - Google Patents
Synthese von hydrophoben alkoxylierten Polymeren Download PDFInfo
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- EP0466392B1 EP0466392B1 EP91306039A EP91306039A EP0466392B1 EP 0466392 B1 EP0466392 B1 EP 0466392B1 EP 91306039 A EP91306039 A EP 91306039A EP 91306039 A EP91306039 A EP 91306039A EP 0466392 B1 EP0466392 B1 EP 0466392B1
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- EP
- European Patent Office
- Prior art keywords
- polymer
- amine
- hydrophobic
- alkoxylated
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 230000002209 hydrophobic effect Effects 0.000 title claims description 37
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 229920002214 alkoxylated polymer Polymers 0.000 title 1
- 229920001600 hydrophobic polymer Polymers 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims description 125
- 150000001412 amines Chemical class 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 17
- 150000003141 primary amines Chemical class 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000012429 reaction media Substances 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940059260 amidate Drugs 0.000 claims 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims 1
- 150000003335 secondary amines Chemical class 0.000 claims 1
- 238000001212 derivatisation Methods 0.000 description 25
- 239000000178 monomer Substances 0.000 description 21
- -1 alkali metal salts Chemical class 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 19
- 239000000376 reactant Substances 0.000 description 19
- 239000007858 starting material Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 14
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 10
- 239000012431 aqueous reaction media Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000007112 amidation reaction Methods 0.000 description 6
- 125000001165 hydrophobic group Chemical group 0.000 description 6
- 229910052757 nitrogen Chemical group 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 5
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BJSKBZUMYQBSOQ-UHFFFAOYSA-N Jeffamine M-600 Chemical compound COCCOCC(C)OCC(C)OCC(C)OCC(C)OCC(C)OCC(C)OCC(C)OCC(C)OCC(C)N BJSKBZUMYQBSOQ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000011938 amidation process Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000007056 transamidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Definitions
- the present invention is in the technical field of polymer synthesis by post-polymerization derivatization.
- Polymers prepared by the polymerization of relatively simple, ethylenically-unsaturated monomers such as (meth)acrylic acid and its esters, (meth)acrylamide, maleic anhydride or maleic acid, crotonic acid and its esters, methyl vinyl ether, vinyl acetate, acrylonitrile, styrene and the like, are well known and are relatively easy to prepare by polymerization techniques well known in the art.
- the preparation of polymers that contain hydrophobic pendant groups by the polymerization of ethylenically-unsaturated monomers which contain such hydrophobic groups using conventional polymerization techniques is limited by the availability of such monomers and possible complications arising in the attempt to incorporate such monomers into the polymer during the polymerization. Complications during the polymerization may well occur if the hydrophobe-containing monomer does not have solubility characteristics that are compatible with the desired polymerization technique(s).
- Post-polymerization derivatization of polymers prepared by conventional polymerization techniques using relatively simple and readily available monomers, whereby a mixture of pendant hydrophobic groups and pendant alkoxylated groups, are introduced into the polymer avoids the difficulties regarding monomer availability and the complications encountered in incorporating such unusual monomers during a polymerization reaction.
- Such a post-polymerization process is highly desirable if it is economically efficient. Economic efficiency is dependent upon many variables, including the efficiency with which the process proceeds, the reasonableness of the reaction conditions required, the availability of both the basic polymer(s) to be derivatized and the derivatizing agent(s), the use of a minimum of reaction steps and the ease at which the end product polymer can be recovered from the reaction mixture.
- Polymers having unique mixtures of pendant hydrophobic groups and pendant alkoxylated groups are highly desirable given the unique properties imparted to the polymer by the combinations of such diverse groups.
- a minimum number of reaction steps is desirable as is also minimum time required for the derivatization.
- the process should preferably proceed under relatively mild reaction conditions and minimize any deleterious effects on the polymer structure.
- the present invention also provides a unique polymer having incorporated thereinto mixtures of hydrophobic and alkoxylated pendant groups.
- the present invention provides a method of preparing polymers having bonded to the polymer backbone pendant groups having the structural formula wherein n is zero or an integer of 1 to 10, R1 is (over the whole polymer) a mixture of both hydrophobic groups and alkoxylated groups and R is hydrogen or substituent other than hydrogen, by derivatization of a pre-existing polymer with at least one amine, in a substantially homogeneous reaction mixture at an elevated temperature for a time sufficient for (trans)amidation to occur.
- the derivatization process employs pre-existing polymers that contain pendant groups having the structure of Formula I: wherein n is zero or an integer from 1 to about 10, and X is -NH2, -OH, or -O-, and salts thereof, and mixtures or combinations of such pendant groups.
- salts alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and, alkanol amine salts.
- the derivatization process employs as the source of hydrophobic and alkoxylated radicals,primary and secondary amines containing the desired radical(s).
- the reaction mixture is comprised of the reactants, i.e. , the polymer(s) and the amine(s), and a reaction medium in which the reactants are soluble or substantially homogenously dispersible.
- a reaction medium in which the reactants are soluble or substantially homogenously dispersible.
- an aqueous reaction medium is employed.
- the pendant groups subject to derivatization are contained in a polymer "unit” or “mer unit” (a segment of the polymer having two adjacent backbone carbons) having the structure of Formula II: wherein R1, R2 and R3 are independently hydrogen or substituent other than hydrogen and wherein Y is the pendant group(s) the structure of which is defined above by Formula I.
- substituted is meant herein a single or multivalent radical other than hydrogen covalently bonded to a carbon or nitrogen of the referenced molecule.
- R1, R2 and/or R3 of Formula II above are substituents other than hydrogen, typically they are C1 ⁇ 4 alkyl or carboxylic substituents.
- the derivatization process is a (trans)amidation reaction whereby the hydrophobic and alkoxylated radicals of the end product polymer are substituents to the nitrogen of an acid amide group, as discussed in more detail below.
- the present invention also provides unique polymers that contain both hydrophobic and alkoxylated pendant groups which are substituents to the nitrogen of an acid amide group, as discussed in more detail below.
- the polymers employed in the derivatization process contain pendant groups having the structure of Formula I above and include pendant groups having carboxyl, carboxylate, and acid amide moieties. Such moieties are the reactive groups that enter the (trans)amidation reaction with the amine derivatiziting agents. There is no theoretical minimum of mer units containing such groups required of the polymer employed and the derivatization theoretically can be accomplished with as little as one such mer unit per polymer molecule.
- the starting material polymer should have 10 mole percent or more of mer units containing the pendant groups having the structure of Formula I above.
- Ethylenically-unsaturated monomers that provide to a polymer pendant groups having the structure of Formula I include (meth)acrylamide, (meth)acrylic acid and salts thereof, crotonic acid, maleic acid, maleic anhydride and other monomers, for instance acrylonitrile, (meth)acrylic acid esters, and the like, that may be converted into mer units having the desired final pendant groups after incorporation into the polymer, for instance by hydrolysis.
- Polymers that may be employed in the derivatization process may contain any amount of mer units other than those providing pendant groups of Formula I above,provided that such other mer units do not comprise the entirety of the polymer. As mentioned above, however, it is believed that to achieve a favorable reaction without employing any significant excess of derivatizing agent, and to provide an end product polymer having a reasonable degree of properties derived by virtue of the derivatization, the amount of mer units not providing pendant groups of the Formula I'above should not exceed about 90 mole percent.
- any monomer that is polymerizable with the monomers providing pendant groups of the Formula I above may be incorporated into the polymer, although considerations such as ease of polymerization of the given monomer mixture, and the propensity of the comonomers to engage in side reactions or interfere with the derivatization reaction, may be factors in the selection of comonomers.
- vinyl acetate is generally considered a good comonomer with maleic anhydride but not with acrylic acid, and hence its desirability as a comonomer is dependent upon the type of monomer that will be providing the necessary pendant groups.
- Other good comonomers with maleic anhydride are methyl vinyl ether or styrene.
- Good comonomers with acrylic acid and acrylamide include the alkyl esters of acrylic acid and acrylonitrile.
- Other possible considerations concerning the selection of suitable comonomers are the properties of the starting material polymer and the end material polymer. For instance, a hydrophilic comonomer may be preferred when it is desired to increase the water solubility of the starting material polymer and/or the end material polymer, or a hydrophobic comonomer may be selected to decrease water solubility when desired.
- An amount of butyl acrylate may be used as a comonomer to provide a degree of tack to the end product polymer.
- One comonomer may be more advantageous than another if the monomer itself is less toxic and the toxicity of residual monomer in the end product polymer is a consideration for the intended use of the polymer.
- the starting material polymer may be a random polymer, or other than a random polymer.
- the derivatizing agents are mixtures of primary and/or secondary amines having a hydrophobe radical, with primary and/or secondary amines having alkoxylated radicals.
- the methyl radical of methyl amine is a hydrophobic radical, particularly considering the diminished hydrophilicity when a pendant acid amide group (-CONH2) is derivatized to an N-substituted methyl amide group (CONHCH3).
- Hydrocarbon radicals having three or more carbon atoms are significantly hydrophobic for purposes of the present invention, and hydrophobic radical having 12 or more carbon atoms are preferred for some purposes of the present invention.
- the hydrophobic radical need not be saturated, and for some purposes of the present invention a degree of carbon-to-carbon unsaturation is preferred for long-chain hydrophobic radicals.
- the hydrophobic radical may contain other substituents provided that such substituents do not destroy the hydrophobic nature of the radical. While primary amines are preferred, the use of secondary amines is not excluded.
- Alkoxylated radicals generally contain ethoxy (-CH2CH2O-) groups or propoxy (-CHCH3CH2O-) groups, generally derived from ethylene oxide and propylene oxide, or mixtures of both types of alkoxy groups.
- the alkoxylated amine derivatizing agent should contain an amino group, preferably a primary amino group, and at least one alkoxyl group, and may contain other groups, for instance hydrocarbon groups.
- a very useful group of commercially available alkoxylated primary amines are sold by the Texaco Chemical Company under the tradename of "Jeffamine".
- Jeffamine M-600 has the following structure: As seen from the structural formula above, Jeffamine M-600 contains both ethoxy and propoxy groups and is reported to have more than 1.71 meq/g of primary amine.
- Another Jeffamine product having a mixture of ethoxy and propoxy groups is Jeffamine M-1000 which has the following structure: As seen from the use of fractional subscripts in the structural formula above, Jeffamine M-1000 is a mixture of linear polyether amines varying somewhat in their total ethoxy and propoxy groups.
- Jeffamine M-1000 is reported to have a total amine content of 0.85 meq/g and a primary amine content of 0.83 meq/g.
- Jeffamine M-300 and Jeffamine M-360 both contain a reasonably significant hydrocarbon group.
- Jeffamine M-300 has the structure of: wherein R4 is a mixture of linear C10 to C12 alkyl groups and x has an average value of 1.
- Jeffamine M-360 has the structure of: and has a total amine content of greater than 2.47 meq/g and a primary amine content of greater than 2.39 meq/g.
- alkoxylated primary amines are sold by the Texaco Chemical Company under the tradename of "Surfonamine MNPA" (Surfonamine is a trademark of the Texaco Chemical Company) and this series of alkoxylated amines has the general structural formula of: wherein m, the number of ethoxy radicals per molecule,varies from about 1 to about 12, and n, the number of propoxy radicals per molecule, varies from about 1 to about 4, for the various amines of the series, i.e. , Surfonamine MNPA-380, 510, 750, and 860. These nonylphenol alkoxylated primary amines contain both a hydrocarbon chain and an aromatic radical, in addition to the alkoxy and amine radicals.
- alkoxylated amine is meant herein generally an amine, either primary or secondary, having at least on alkoxy radical, either ethoxy or propoxy, within its chemical structure.
- the alkoxylated amine is an amine wherein the alkoxy radical(s) comprise at least one percent of the amine's formula weight.
- the alkoxylated amine is an amine wherein the alkoxy radical(s) comprise at least five percent of the amine's formula weight, and in even more preferred embodiment, at least ten percent of the amine's formula weight.
- a useful group of hydrophobic radical containing amines are the aliphatic amines commercial available under the tradename of "Armeen” from Armak Chemicals ("Armeen” is a registered trademark of Akzo Chemie America for the aliphatic amines produced by Armak Chemicals).
- Armeen primary amines are soyaamine (C18H35NH2) sold under the tradenames of Armeen S and Armeen SD.
- Armeen SD has a water solubility (in percent of solution weight) of about 10.13 at 50° C and 4.01 at 80° C. It has a primary amine content of 98% and a secondary amine content of 2% (ASA).
- Armeen primary amines are Armeen HTD, a hydrogenated tallow amine (C18H37NH2) having a water solubility of 4.39 at 80° C (a nonfluid mixture in water at 60° C),Armeen 16D, a hexadecylamine (C16H33NH2) which has a water solubility of 12.99 at 60° C. and 5.47 at 80° C, and Armeen 12D, a dodecylamine (C12H25NH2), which is a liquid at 25° C, and has a water solubility of 24.35 at 50° C and 12.50 at 80° C.
- C18H37NH2 a hydrogenated tallow amine having a water solubility of 4.39 at 80° C (a nonfluid mixture in water at 60° C)
- Armeen 16D a hexadecylamine (C16H33NH2) which has a water solubility of 12.99 at 60° C. and 5.47 at 80° C
- Armeen secondary amines are Armeen 2C, a dicocoamine (C12H25)2NH, a solid at 25° C,and Armeen 2HT, a di(hydrogenated-tallow)amine, (C18H37)2NH2, which is also solid at 25° C.
- the (trans)amidation process is conducted in an aqueous medium.
- the use of an aqueous medium is generally less expensive than a nonaqueous medium.
- the end product polymer is easier to isolate from an aqueous medium.
- An aqueous medium moreover minimizes the toxicity of the reaction mixture, and the toxicity of the end product polymer if not completely isolated from the reaction medium.
- the end product polymer isolation step may not be required. While all of such advantages ensue from the use of an aqueous reaction medium, the employment of an aqueous reaction medium heretofore would generally be considered contrary to the objectives of obtaining a reasonable degree of derivatization and an economically efficient process.
- the present invention does not, in its broadest definition, exclude the use of nonaqueous reaction mediums, for instance dimethyl sulfoxide (“DMS”) or various other organic liquids.
- DMS dimethyl sulfoxide
- the reactants should be soluble or substantially homogeneously dispersible in the reaction medium employed, given the concentrations of reactants used.
- Hydrophobe-containing amine reactants having some degree of carbon-to-carbon unsaturation within the hydrophobic moiety are generally more fluid than the equivalent fully saturated amines and such fluidity facilitates dispersing such reactants in the reaction medium, particularly when the medium is water.
- concentration of the reactants in such process can of course be lowered if needed for to disperse the reactants.
- the water solubility or water dispersibility characteristics of the starting material polymer are dependent upon the balance between its hydrophobic and hydrophilic pendant groups, and its molecular weight, and thus while in some instances one can select the starting material polymer so as to provide the desired degree of water solubility, in other instances the preference for a given polymer is an overriding factor.
- a preferred concentration of the polymer in the reaction mixture is at least ten weight percent, more preferably twenty weight percent.
- the starting reaction mixture need not even be fluid at room temperature.
- the end product polymer even when an aqueous reaction medium is employed may possibly not be water soluble or water dispersible.
- the (trans)amidation reaction is conducted at elevated temperatures and preferably under pressures that exceed atmospheric pressure.
- the reaction generally is accomplished in a closed vessel at a temperature of from about 120° C. to about 200° C.
- the starting material polymer may contain participating pendant groups that are wholly acid amide groups, for instance the pendant groups of (meth)acrylamide mer units, or that are wholly carboxylic groups, for instance the pendant groups of (meth)acrylic acid or maleic anhydride mer units. If the former situation existed, the process would be considered a transamidation reaction whereby acid amide groups are derivatized by amine reactants to N-substituted acid amide groups. If the latter situation existed, the process would be considered an amidation reaction whereby carboxylic groups would be derivatized by amine reactants to N-substituted acid amide groups. Hence the process is deemed a (trans)amidation reaction, and it has been found that the derivatization proceeds extremely efficiently when the starting material polymer contains a mixture of both carboxylic groups and acid amide groups.
- the derivatization reaction generally does not proceed to the exhaustion of all of the derivatizing amine employed, and hence it is desirable to use a greater charge of amine reactant than stoichiometrically required for the desired degree of derivatization.
- a one to one mole ratio of participating polymer pendant groups to derivatizing amine possibly may be used, and in fact less participating pendant groups and amine reactant, on a mole basis, may be reasonably used.
- the derivatization reaction should be permitted to proceed for at least a one-half hour duration, and preferably for a time period of from about three to about eight hours.
- the derivatization process was conducted using a concentration of starting material polymer of from about 20 to about 32 weight percent based on the entire reaction mixture (polymer, derivatizing agent and water medium).
- concentration of starting material polymer on such basis is at least 20 weight percent, although a reasonably efficient process ensues when the concentration of the starting material polymer is as low as 10 weight percent, same basis.
- concentration of starting material polymer may fall to as low as 5 weight percent or less.
- the concentration of the end material polymer in the reaction mixture is of course dependent on the amount of derivatizing agent employed and the degree of reaction, in addition to the initial polymer concentration.
- the starting material polymer's concentration was about 31 weight percent
- the end material polymer's concentration was about 43 weight percent.
- the starting material polymer must contain pendant groups having the structure of Formula I above.
- Such pendant groups contain either a carboxylic radical (wherein X of Formula I is -OH and/or -O ⁇ ) or an acid amide radical (wherein X of Formula I is -NH2).
- the mole ratio of carboxylic radical containing pendant groups to acid amide containing pendant groups in the starting material polymer is at most 1:9, and in more preferred embodiment is at most 1:3.
- the unique polymers of the present invention contain both hydrophobic and alkoxylated groups which are substituents to the nitrogen of pendant acid amide groups.
- the presence of these diverse groups within the same polymer provides unique characteristics for various end use applications. For instance, when used in water systems, both types of pendant groups may have a propensity to attach to substrates.
- the hydrophobic moieties will tend to attach to substrates by virtue of their hydrophobic nature, while the alkoxylated moieties may tend to attach to substrate surfaces due to hydrogen bonding mechanisms.
- the presence of both types of side chains provides unique thickening characteristics.
- the polymer may contain as little as 0.1 mole percent of each type of group, based on total moles of mer units in the polymer.
- the polymer contains at least 1 mole percent of each type of group (hydrophobic moiety and alkoxylated moiety), based on total moles of mer units in the polymer.
- the polymer contains at least 2.5 mole percent of each type of group, same basis.
- the molecular weight of the starting material pre-existing polymer is limited to about no more than 200,000, and in some instances, for instance if a homopolymer of acrylamide is used, to no more than 100,000 (weight average molecular weight).
- the starting material polymer is of rather low molecular weight, for instance no more than 50,000, and more preferably no more than about 25,000, and the preference for such low molecular weight starting material preexisting polymers is particularly germane to the unique polymers having both hydrophobic and alkoxylated groups from which unique end use characteristics flow.
- the molecular weight of the starting material polymer is at least about 2,000 (weight average molecular weight).
- the degree of derivatization desired is to incorporate at least 0.1 mole percent of derivatized groups into the polymer, based on total moles of mer units in the polymer, and more preferably to incorporate at least 1 mole percent of the derivatized groups into the polymer, same basis.
- the mole ratio of reactants, i.e. , pendant polymer groups having the structure of Formula I above (participating pendant groups) to the amine-containing derivatizing agent(s) is from about 50:1 to about 1:2, and in more preferred embodiment is from about 50:1 to about 1:1.
- An acrylic acid/acrylamide copolymer having a weight average molecular weight of about 16,000 was derivatized by reaction with both soya-amine and an alkoxylated amine (primary amine) in a single reaction as follows. To 165 grams of a 35 weight percent aqueous solution of the copolymer was added 11.9 grams of the soya-amine (Armeen S) and 40.38 grams of the alkoxylated amine (Jeffamine M-1000 which is described above). This admixture was placed into a 300 ml. Parr reactor. The reactor was purged with nitrogen, then sealed, heated internally to 150° C., and held at that temperature for a 5 hour reaction period.
- the reaction mixture recovered from the cooled reactor had a paste-like consistency. Based on L.C. analysis for residual amine, the soya-amine was determined to have reacted to the extent of 95 weight percent of its initial charge, and the alkoxylated amine was determined to have reacted to the extent of 83 weight percent of its initial charge.
- Example 1 was repeated except the amount of the copolymer solution was decreased to 135 grams, the charge of the soya-amine was increased to 18.31 grams, and the charge of the alkoxylated amine was increased to 66.08 grams.
- the reaction mixture recovered was again of paste-like consistency. Based on L.C. analysis for residual amine, the soya-amine was determined to have reacted to the extent of 86 weight percent of its initial charge and the alkoxylated amine was determined to have reacted to the extent of 58 weight percent of its initial charge.
- An acrylamide homopolymer having a weight average molecular weight of about 7,500 was derivatized as follows. To 170 grams of a 33 weight percent aqueous solution of the polyacrylamide was added 39.51 grams of Jeffamine M-1000 and 10.94 grams of Armeen S, both of which are described above. These amounts were a 5 mole percent charge of both the Jeffamine M-1000 and Armeen S based on the total number of mer units in the polymer charge. This admixture was placed into a 300 ml. Parr reactor. The reactor was purged with nitrogen, then sealed, heated internally to 150° C., and held at that temperature for a 5 hour reaction period. The reaction mixture recovered from the cooled reactor was a brown liquid. Based on L.C. analysis for residual amine, the soya-amine (Armeen S) was determined to have reacted to the extent of 38 weight percent of its initial charge, and the alkoxylated amine was determined to have reacted to zero weight percent of its initial charge.
- Example 3 was repeated except the amount of the polyacrylamide solution was decreased to 135 grams, and the mole percent charges of both the soya-amine and alkoxylated amine were increased to 10 mole percent (62.75 grams of Jeffamine M-1000 and 17.38 grams of Armeen S).
- the reaction mixture recovered again was a brown liquid, and based on L.C. analysis for residual amine, the soya-amine was determined to have reacted to the extent of 34 weight percent of its initial charge and the alkoxylated amine was determined to have reacted to the extent of zero weight percent of its initial charge.
- the present invention is applicable to the industries requiring agents for thickening and soil release, wherein the polymers having pendant hydrophobic and alkoxylated groups are useful.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Claims (24)
- Verfahren zur Herstellung eines Polymers mit am Polymer-Rückgrat gebundenen Seitengruppen der Strukturformel:das zumindest im wesentlichen homogene Dispergieren eines bereits bestehenden Polymers und zumindest eines Amins in einem Reaktionsmedium zur Bildung eines im wesentlichen homogenen Reaktionsgemisches,wobei das bereits bestehende Polymer beteiligte Seitengruppen der folgenden Strukturformel aufweistwobei das Amin aus mit hydrophoben und alkoxylierten Resten mischsubstituierten primären und/oder sekundären Aminen besteht,und das Umsetzen des bereits bestehenden Polymers mit dem Amin bei erhöhter Temperatur und über eine Zeitspanne, die ausreicht, um zumindest einige der beteiligten Seitengruppen des bereits bestehenden Polymers mit den Aminen zu (trans)amidieren.
- Verfahren nach Anspruch 1, worin das Reaktionsmedium wäßrig ist.
- Verfahren nach Anspruch 1 oder 2, worin das bereits bestehende Polymer zumindest 10 Mol-% Mereinheiten enthält, die die beteiligten Seitengruppen aufweisen.
- Verfahren nach einem der vorhergehenden Ansprüche, worin der hydrophobe Rest zumindest drei Kohlenstoffatome enthält.
- Verfahren nach Anspruch 4, worin der hydrophobe Reste zumindest zwölf Kohlenstoffatome enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, worin das Amin im wesentlichen primäres Amin ist.
- Verfahren nach einem der vorhergehenden Ansprüche, worin das Amin mit alkoxylierten Substituenten ein Amin ist, worin die Alkoxyreste zumindest 5% des Formelgewichts des Amins ausmachen.
- Verfahren nach Anspruch 7, worin die Alkoxyreste zumindest 10% des Formelgewichts des Amins ausmachen.
- Verfahren nach einem der vorhergehenden Ansprüche, worin die Konzentration des bereits bestehenden Polymers im Reaktionsgemisch zumindest 10 Gew.-% beträgt.
- Verfahren nach Anspruch 9, worin die Konzentration des bereits bestehenden Polymers im Reaktionsgemisch zumindest 20 Gew.-% beträgt.
- Verfahren nach einem der vorhergehenden Ansprüche, worin das Molverhältnis der beteiligten Seitengruppen mit einer Formel, worin X = -OH und/oder -O⁻ ist, zu den beteiligten Seitengruppen mit einer Formel, worin X = -NH₂ ist, zumindest 1:9 beträgt.
- Verfahren nach Anspruch 11, worin das Molverhältnis zumindest 1:3 beträgt.
- Verfahren nach einem der vorhergehenden Ansprüche, worin zumindest 0,1 Mol-% oder des Gemisches aus hydrophoben und alkoxylierten Resten, bezogen auf die gesamten Mereinheiten, in das vorliegende Polymer substituiert werden.
- Verfahren nach einem der vorhergehenden Ansprüche, worin das Molverhältnis der beteiligten Seitengruppen zum Amin im Reaktionsgemisch etwa 50:1 bis etwa 1:2 beträgt.
- Verfahren nach einem der vorhergehenden Ansprüche, worin das bereits bestehende Polymer ein durchschnittliches Molekulargewicht von bis zu 50.000 aufweist.
- Verfahren nach einem der vorhergehenden Ansprüche, worin das vorliegende Polvmer ein Polymer ist, das Acrylsäure- und Acrylamid-Mereinheiten enthält.
- Polymer nach Anspruch 17, worin der hydrophobe Rest zumindest drei Kohlenstoffatome enthält.
- Polymer nach Anspruch 18, worin der hydrophobe Rest zumindest zwölf Kohlenstoffatome enthält.
- Polymer nach einem der Ansprüche 17 bis 19, worin die Alkoxyreste innerhalb des alkoxylierten Rests zumindest 5% des Formelgewichts des alkoxylierten Rests ausmachen.
- Polymer nach einem der Ansprüche 17 bis 20, worin das Polymer zumindest 1 Mol% an Mereinheiten mit den einen hydrophoben Rest enthaltenden Seitengruppen und zumindest 1 Mol-% an Mereinheiten mit den einen alkoxylierten Rest enthaltenden Seitengruppen enthält.
- Polymer nach Anspruch 21, worin das Polymer zumindest 2,5 Mol-% an Mereinheiten mit den einen hydrophoben Rest enthaltenden Seitengruppen und zumindest 2,5 Mol-% an Mereinheiten mit den einen alkoxylierten Rest enthaltenden Seitengruppen enthält.
- Polymer nach einem der Ansprüche 17 bis 22, worin das Molekulargewicht des Polymers ohne hydrophobe und alkoxylierte Reste bis zu 50.000 beträgt.
- Polymer nach einem der Ansprüche 17 bis 23, worin das Molekulargewicht des Polvmers ohne hydrophobe und alkoxylierte Reste bis zu 25.000 beträgt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US548838 | 1983-11-04 | ||
US07/548,838 US5075390A (en) | 1990-07-06 | 1990-07-06 | Synthesis of hydrophobic/alkoxylated polymers |
Publications (3)
Publication Number | Publication Date |
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EP0466392A2 EP0466392A2 (de) | 1992-01-15 |
EP0466392A3 EP0466392A3 (en) | 1992-06-17 |
EP0466392B1 true EP0466392B1 (de) | 1996-05-15 |
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ID=24190598
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Application Number | Title | Priority Date | Filing Date |
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EP91306039A Expired - Lifetime EP0466392B1 (de) | 1990-07-06 | 1991-07-03 | Synthese von hydrophoben alkoxylierten Polymeren |
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Country | Link |
---|---|
US (1) | US5075390A (de) |
EP (1) | EP0466392B1 (de) |
DE (1) | DE69119490T2 (de) |
ES (1) | ES2089135T3 (de) |
Families Citing this family (9)
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US6482373B1 (en) | 1991-04-12 | 2002-11-19 | Newmont Usa Limited | Process for treating ore having recoverable metal values including arsenic containing components |
US5332559A (en) * | 1991-07-10 | 1994-07-26 | Newmont Gold Co. | Biooxidation process for recovery of metal values from sulphur-containing ore materials |
US6696283B1 (en) | 1991-07-10 | 2004-02-24 | Newmont Usa Limited | Particulate of sulfur-containing ore materials and heap made therefrom |
US6383458B1 (en) | 1991-07-10 | 2002-05-07 | Newmont Mining Corporation | Biooxidation process for recovery of metal values from sulfur-containing ore materials |
DE4308773C2 (de) * | 1992-07-24 | 1996-05-09 | Goldschmidt Ag Th | Umgeesterte Polyacrylsäureester mit Ammonium- und Polyoxyalkylen-Gruppen und ihre Verwendung in Trennmitteln |
DE10207277A1 (de) * | 2002-02-21 | 2003-09-04 | Basf Ag | VOC-arme Fettungsmittel, ihre Verwendung in der Herstellung und/oder Behandlung von Leder und Häuten, sowie Verfahren zur Herstellung und/oder Behandlung von Leder und Häuten mit diesen Fettungsmitteln |
DE10320110A1 (de) | 2003-05-06 | 2004-11-25 | Basf Ag | Fettungsmittel zur Herstellung und Behandlung von Leder |
EP1735414A2 (de) * | 2004-01-30 | 2006-12-27 | Huntsman Petrochemical Corporation | Oberflächenaktive polymere als detergentien |
BR112015005866A2 (pt) | 2012-09-19 | 2017-07-04 | Dow Global Technologies Llc | método para funcionalizar um produto polimérico com funcionalidade amida e método para preparar um produto polimérico com funcionalidade amida |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3474003A (en) * | 1965-12-08 | 1969-10-21 | Hirsch Abraham A | Combination sample-culture bottle for bacteriological tests |
US3503946A (en) * | 1967-07-14 | 1970-03-31 | American Cyanamid Co | Process for the manufacture of cationic polyacrylamide |
US3478003A (en) * | 1968-05-13 | 1969-11-11 | Dow Chemical Co | Cationic polyacrylamide terpolymers |
US4139689A (en) * | 1972-02-24 | 1979-02-13 | Sandoz Ltd. | Polymeric basic amides |
NL7304931A (de) * | 1972-04-11 | 1973-10-15 | ||
DE2535660A1 (de) * | 1975-08-09 | 1977-02-17 | Cassella Farbwerke Mainkur Ag | Verfahren zur herstellung vernetzbarer polymerisate und copolymerisate |
FR2378808A1 (fr) * | 1977-01-28 | 1978-08-25 | Mar Pha Etu Expl Marques | Nouveaux copolymeres hydrophiles a base de n-(tris(hydroxy-methyl)methyl)acrylamide ou de n-(tris (hydroxymethyl)methyl)methacrylamide, leur preparation et leur emploi dans les techniques de separation |
US4297226A (en) * | 1978-06-19 | 1981-10-27 | Texaco Development Corp. | Process for secondary recovery |
US4326969A (en) * | 1978-10-23 | 1982-04-27 | Texaco Development Corp. | Process for secondary recovery |
US4596858A (en) * | 1981-11-27 | 1986-06-24 | Gregor Harry P | Solid state cross-linked polymer |
CA1225439A (en) * | 1983-11-14 | 1987-08-11 | Anchor Hocking Corporation | Method and means for forming lines of weakness in closure caps and similar articles using a laser beam |
DE3680426D1 (de) * | 1985-08-12 | 1991-08-29 | Allied Colloids Ltd | Dispergiermittel. |
FR2592885B1 (fr) * | 1986-01-10 | 1988-08-05 | Elf Aquitaine | Nouveaux polymeres du type polyamide-n-substitue, leur procede de preparation et leur emploi comme additifs pour huiles brutes de petrole |
US4885345A (en) * | 1986-02-24 | 1989-12-05 | Nalco Chemical Company | Alkoxylated/cationically modified amide-containing polymers |
US4731419A (en) * | 1986-02-24 | 1988-03-15 | Nalco Chemical Company | Alkoxylated/cationically modified amide-containing polymers |
US4921903A (en) * | 1988-10-11 | 1990-05-01 | Nalco Chemical Company | Process for preparing high molecular weight hydrophobic acrylamide polymers |
-
1990
- 1990-07-06 US US07/548,838 patent/US5075390A/en not_active Expired - Fee Related
-
1991
- 1991-07-03 EP EP91306039A patent/EP0466392B1/de not_active Expired - Lifetime
- 1991-07-03 DE DE69119490T patent/DE69119490T2/de not_active Expired - Fee Related
- 1991-07-03 ES ES91306039T patent/ES2089135T3/es not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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US5075390A (en) | 1991-12-24 |
EP0466392A2 (de) | 1992-01-15 |
EP0466392A3 (en) | 1992-06-17 |
ES2089135T3 (es) | 1996-10-01 |
DE69119490T2 (de) | 1996-10-31 |
DE69119490D1 (de) | 1996-06-20 |
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